PFAS Technical Group October 15, 2021

Agenda

• Welcome and Introductions

• Michigan Airport Grant & Sampling Initiative – Mike Jury, MI

• Validation of Fluorine-Free AFFF against Military SpecificiationPerformance Criteria – Satya Chauhan, Battelle Memorial Institute

• Conclusions & Next Steps

Wisconsin DNR’s PFAS Technical Group -Michigan Airport ResultsOctober 15, 2021

Mike Jury, PFAS Specialist

Remediation and Redevelopment Division

(517) 242-9578

JuryM1@Michigan.gov

Review of Potential Aviation Sources/Release Locations

• AFFF

• Fire Training Areas

• Fire Stations

• Emergency Response Location

• WWTP Facilities

• Landfills

• Maintenance Shops

• Hydraulic Oils

• Storage Areas

• Surface Drainage

• Spray Test Areas

• Hangars

Potential AFFF Sources at Airports

Sampling Considerations

• Purpose

• Locations

• Procedures

• Analytical Methods

Sampling Considerations

• Purpose

•Nature of Investigation

• Extent of Investigation

• Potential Pathways

• Drinking Water, Groundwater, Surface Water, Storm Water

• Soil Movement

Sampling Considerations

• Locations

•Historic Use Areas

• Accident Areas

• Storm Water

•Movement of soils on property can create multiple locations

Sampling Considerations

• Procedures

•Quantification levels - how low?

•How many compounds to sample for - what method?

• Cross contamination from decontamination water -sample it before you use it

•QA/QC, how about that QAPP?

Sampling Considerations• Analytical Methods to Consider

• EPA 537.1 and EPA Method 533 (Drinking Water)

• LC MS/MS, Isotope Dilution Method (all other media)

• ASTM D7979 (water)

• ASTM D7968 (soil)

•DOD QSM 5.3 (QA protocol)

Michigan PFAS

Groundwater Clean-up Criteria

and Drinking Water Standards

Compound

Michigan Standards

PFNA 6 ppt

PFOA 8 ppt

PFOS 16 ppt

PFHxS 51 ppt

GenX

(HFPO-DA) 370 ppt

PFBS 420 ppt

PFHxA 400,000 ppt

• MI awarded grants to 19 airports in the fall 2020 to conduct testing at commercial services airport

• Up to $250,000 grant per airport

• Two rounds (RFPs) were done to allocate the funds

• Grants had two conditions:• Had to submit Phase 1 results and proposed phase 2 plans to MDOT

and EGLE for review/approval• Had to follow EGLE sampling protocols

• Grant funds were generally used for soil, groundwater, and storm water sampling on-site

• In some cases, EGLE sampled residential wells, groundwater, and surface water around the airports

Michigan Airport Grants

On-Site Investigations

• One entity did not follow all protocols – used an untested hose for decon water

• Otherwise, having the 2 grant requirements worked well

• Recommend having a Phase 1 results call with the airport, contractor, remediation and water staff; discuss proposed phase 2 work, too

• If AFFF was used to fight a fire/accident, for training or testing, or was spilled, you can expect to find it in soil, groundwater or surface water

Michigan Airport Grants - Findings

• Highest groundwater result was 730,000 ppt PFOS

• Highest storm water result was 9,100 ppt PFOS

• Surface water sampling was done by EGLE staff near many of the 19 airports

• EGLE sampled res wells adjacent to all of these airports if any were found to exist after reviewing res well data in a state-wide database and in consult with the local Health Department

• DHHS and local health lead the health response (notifications, bottled water, filter units) for res well sampling

Michigan Airport Grants - Findings

Off-Site Investigations

Next Steps

• Airport grants need to be finished by early spring 2021

• Airports will have ongoing obligations to delineate plumes, address storm water issues per any storm water permits, and conduct interim responses/remediation efforts

MICHIGAN PFAS ACTION RESPONSE TEAM

(MPART)www.Michigan.gov/PfasResponse

Dr. Satya P. Chauhan

Senior Program Director

Chauhan@Battelle.org

Presented to Wisconsin Dept. of Natural Resources

October 15,2021

Progress in Enhancing Performance of PFAS-free Foams (PFFs) against Military Specification Criteria

1

Agenda

• SERDP and ESTCP R&D program on replacing AFFF for

military applications

• Objectives of ESTCP-funded Battelle Projects

• PFF products and vendors

• Results for environmental, corrosion, and other properties

• Selected technologies to enhance firefighting performance

▪ Compressed Air Foam (CAF); Ultra High Pressure (UHP); Additives

• Firefighting performance data

• Key points and future plans

2

SERDP and ESTCP Programs on AFFF Replacement for Firefighting• SERDP is supporting R&D on emerging PFFs that have

better firefighting performance than COTS PFFs

▪ Initiated evaluation of toxicity of COTS and emerging PFFs

▪ Just initiated R&D program to develop functional additives to

enhance performance of PFFs

• ESTCP is funding validation testing of COTS and maturing

PFFs as well as alternative foam delivery technologies

• Supporting compliance with NDAA of FY20

▪ Prohibition on use of AFFF for on-shore use beginning Oct 1, 2024

▪ Navy to publish new Mil-Spec for PFFs by Jan 31, 2023 and ensure

that such agents are available no later than Oct 1, 2023

3

Objectives of Battelle’s Projects

• Assessment, optimization, and demonstration of

16+ mature PFFs against MIL-PRF-24385F

• Assessment including▪ Environmental (LC50, IC25)

▪ Corrosivity

▪ Fire Performance (extinguishment time

and burnback time)

• Optimization of PFFs using commonly available technologies▪ Compressed Air Foam (CAF)

▪ Ultra-high Pressure (UHP)

• Demonstration/Validation against military relevant firefighting scenarios

• Technology Transition

4

Candidate PFF Product and Vendor NamesWP19-5299 ESTCP Project WP20-5335 ESTCP Project

Enviro USP 2-3%/ Fomtec® Phos-Chek® FF 1%/ Phos-Chek®

Re-Healing™ 3%/ Solberg Ecopol Premium/ BioEx

Phos-Chek® FF 3-6%/ Phos-Chek® Novel foam/ BioEx

Ecopol A and Ecopol A+/ BioEx Pyrocool®/ Pyrocool

FireAde®/ Fire Service Plus FireBull/ Fire Service Plus

Avio® Green (Jet Foam)/National Foam

(Jet/Angus)

GFFF/ Green Fire

Universal Green/ National Foam Avigard/ Solberg

Novacool UEF/ Novacool FT Slam/ Fire Terminator

5

Performance Objectives

Performance Objective Data Requirements Success Criteria Success Criteria Achieved?

Quantitative Performance Objectives (Laboratory-based Mil-Spec Testing)

CorrosionAs described in MIL-PRF-

24385F

• Corrosion rates for 4

substrates

• 3 PFFs passed all

• 3 PFFs with partial failures

• More being tested

Environmental Impact

• LC50 /IC25

• Ultimate Biological

Oxygen Demand (BOD20)

• Chemical Oxygen

Demand (COD)

• LC50 > 500mg

L

•BOD20

COD< 0.65

• COD < 1,000kmg

L

• No PFF passes

• C6 AFFF does not pass

BOD20/COD

• BOD and COD complete

for 13/16 products

Other Physical Properties

• Viscosity

• Refractive Index

• pH

• Spreading coefficient

(surface and interfacial

tension)

• Viscosity 25℃ > 2 cSt• Viscosity 5℃ < 20 cSt• Refractive Index >

1.3630• pH (7.0-8.5)

• Spreading Coeff > 3

• No PFF meets all

requirements; all fail

spreading coefficient

• Some PFFs are highly

non-Newtonian

• Complete for 13 of 16

products

6

Environmental Impact• LC50 and IC25 data obtained for fathead minnows

• LC50 for as-rec’d PFFs is 50-100 mg/L (EPA Tox Category: Slightly Toxic)

▪ As-delivered foam value is 1,500-3,000 mg/L

• All PFFs fall below the 0.65 BOD20/COD spec (typically 0.3-0.4)

• All PFFs pass the COD requirement of <1,000,000 mg/L

[1] Schaefer, T. (2013). Aquatic Impact of Firefighting Foams [White paper]. Retrieved January 23,

2020 from Solberg Foam: https://www.solbergfoam.com/getattachment/b1698ff8-e0f5-4e09-b3ac-

426a59c4bb7e/WP-Aquatic-Impact-of-AFFF-F-2012007.aspx

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Corrosion and Various Physical Properties

• MIL-SPEC corrosion testing to date indicates that the primary concern is with

failures for the C70600 Cu-Ni coupons for several PFFs

▪ Diluted 10% by volume in seawater; metal coupons submerged for 60 days

• Some products marginally failed specs for physical properties like pH and

refractive index, but these have no bearing on fire performance

• No PFFs have a positive spreading coefficient or exhibit inherent film-forming

behavior; values are 0.0 to minus 5.0 vs. spec of ≥3.0.

• The Mil-Spec requires viscosity of ≥2 cp at 25℃ which all PFFs meet

▪ Some are highly non-Newtonian and far exceed the maximum spec viscosity of 20 cp

at 5℃

8

Firefighting Performance Objectives

Performance Objective Data Requirements Success Criteria Success Criteria Achieved?

Quantitative Performance Objectives (28-ft2 Mil-Spec, Gasoline Fires)

Foamability/Drain TimeAs described n MIL-PRF-

24385F

• 25% foam drain time

≥150 s

• Foam expansion ≥5

• Yes

90% Control • Heat Flux • NA • NA

Fire Extinguishment • Stopwatch• Extinguishment time

≤30 s

• No

Burnback/Cold Burnback• Stopwatch

• Heat flux

• Burnback time ≥360 s • Yes for 5 of 7 PFFs

• Yes for 1 other with CAF

only

Qualitative Performance Objectives (20-ft diameter and 91-ft Diameter Fuel Fires)

Handling/usability • Testing notes• Fire control and

extinguishment

• Yes for 20-ft diameter

9

CAF vs. Air-aspirated Foam

• More uniform bubble distribution influences foam stability

▪ Measured by 25% drain time

Laundess, A. J., et.al., Fire Technology, 47(1), 149-162

10

Site Description-SKY X Fire Hanger

• AFCEC/Tyndall AFB

▪ Located near Panama City, FL

• Mil-Spec Fire Testing

▪ 28-ft2 fires

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Extinguishment Time vs. Foam Delivery Method – E10 Gas• Average reduction of 47% in extinguishment time with

CAF

12

Extinguishment Time vs. Foam Expansion Ratio – Ethanol-free Gas• Average 39% decrease in extinguishment time; optimum near foam

Expansion Ratio (ER) of 12

13

Extinguishment Time– E-free Gas at Optimum Foam Expansion Ratio of 12

• Average ~20 seconds (40%) reduction in extinguishment time (25% w/o PFF 9)

14

Burnback Time for WP20 PFFs –E-free Gas• Average 100% increase in burnback time

• All CAF data at optimum ER of 12

15

Extinguishment time – E-free Gas vs. Jet A Fuel• Extinguishment time for Jet A fire is about 27% lower than for E-Free gas

with CAF at ER 15

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Mil-Spec-scale Testing Summary for PFFs Selected for Large-scale Fire Testing

Product Mil-Spec

Extinguishment

Mil-Spec

Burnback

Optimum CAF

Extinguishment

Optimum

CAF

Burnback

PFF 4 58±7 226±4 50±3 407±26

PFF 6 73±3 565±25 46±7 1088±54

PFF 7 92±5 308±20 46±3 755±32

PFF 8.2 62±8 195±10 46±0 451±26

PFF 12 195±65 198±44 54±.7 Pending

PFF 15 78±14 262±15 49±4 586±29

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Site Description-Silver Flag Training Site• AFCEC/Tyndall AFB

▪ Located near Panama City, FL

• Large Fire Testing

▪ 91-ft diameter (6,504-ft2) fire training pit

▪ Outdoor facilities at Silver Flag training area

▪ Home to RED HORSE (Air Force Rapid Engineer Deployable, Heavy

Operational Repair Squadron)

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Large-scale Fire performance- CAF at 454-ft2 Fire Size• Initial results with Jet-A fire (454-ft2

at 0.053 gpm/ft2 application rate)

▪ PFF 8.2: 33, 32, and 33 seconds

▪ PFF 6: 28, 26, and 28 seconds;

compared to 35 seconds at 28-ft2

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Ultra High Pressure (UHP) Technology

• Truck pressure 1100−1400 psi

▪ Typically uses aspirating nozzle

• Reduces foam application rate

• Small droplet size enhances cooling

effect

▪ Can be combined with dry chemical to

take out three sides of the “Fire

Tetrahedron” at once to improve

firefighting

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Large-scale Fire performance- UHP

• A 454-ft2 fire set up using a 24-ft diameter fire ring was set

up and tested with a P-34 fire truck with UHP capability,

using Jet-A fuel

▪ The extinguishment times with PFF 8.2 were 44, 55, and 82

seconds, at an application rate of 0.030 gpm/ft2 (42% of Mil-Spec

application rate)

▪ The results are encouraging, so we are continuing with testing other

down-selected PFFs

▪ Also plan to test using a smaller, 314-ft2 size to achieve higher

application rates, to see if the fire extinguishment time can be

reduced

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Key points

• No PFFs tested so far meet the Mil-Spec▪ Aquatic, acute toxicity EPA Category: “Slightly Toxic”

▪ Viscosity of several leading products is very high; may require equipment

changes to reduce handling problems

▪ Some products have corrosivity concerns

• All fail fire extinguishment time requirements and a few fail burnback

time requirement▪ Extinguishment times reduced with CAF by and average of 40+%

▪ Burnback times increased with CAF by an average of 100+%, making

several marginal PFFs meet the Mil-Spec

▪ The top 3 products have very similar extinguishment times of ~45 seconds

at optimum CAF conditions and near 30 seconds for Jet A (~35% lower)

• Six (6) PFFs have been down-selected for field-scale testing (PFFs 4,

6, 7, 8.2, 12, and 15), which have extinguishment times in 45-50

seconds range

• Scalability of CAF to 454-ft2 size, for jet fuel, appears looks good so far

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Remaining Testing

• Field-scale testing of CAF on 6 PFFs with Jet A at 6,504-ft2 fire

size

• Additional CAF testing at 314-ft2 scale for 3 products @ 0.071

gpm/ft2

• Exploration of 2-3 newly-developed PFFs, selected from

recent SERDP testing

• Further exploration of best way to utilize UHP benefits

▪ A 314 ft2 (20-ft diameter fire ring) set up ready for testing with E-free gasoline

▪ Need to test at higher than the 0.030 gpm/ft2 explored so far

• Dual-agent testing (PFF plus Purple K) at 314-ft2 fire size with

E-free gasoline

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Acknowledgements

• Dr. Bridgett Ashley (co-PI); AFCEC/Tyndall AFB

• Dr. Heather Luckarift; Battelle

• Malena Maraviglia; Battelle

• Andrew McMeans; Battelle

• Steven Wells; Battelle

• Dr. Robin Nissan; SERDP/ESTCP

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DNR Updates, Conclusions & Next Steps